CN106935707B - A kind of preparation method based on polymer dielectric transport layer perovskite photovoltaic cell - Google Patents

A kind of preparation method based on polymer dielectric transport layer perovskite photovoltaic cell Download PDF

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CN106935707B
CN106935707B CN201710224272.3A CN201710224272A CN106935707B CN 106935707 B CN106935707 B CN 106935707B CN 201710224272 A CN201710224272 A CN 201710224272A CN 106935707 B CN106935707 B CN 106935707B
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transport layer
polymer dielectric
perovskite
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CN106935707A (en
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杨英
张政
郭学益
高菁
潘德群
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Central South University
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Abstract

A kind of preparation method based on polymer dielectric transport layer perovskite photovoltaic cell, comprising the following steps: (1) clean transparent FTO electro-conductive glass, obtain transparent conductive substrate；(2) titanic oxide electronic transport layer is prepared in transparent conductive substrate；(3) perovskite CH is prepared in the titanic oxide electronic transport layer obtained by step (2)3NH3PbX3Extinction layer film；(4) preparation of polymer dielectric transport layer；(5) electrode will be covered in polymer dielectric transport layer.The present invention is using polymer dielectric as hole transmission layer; containing can dissociative ion group in its link units; has many advantages, such as light, easy film forming; the reticular structure of polymer can effectively prevent the volatilization of organic solvent simultaneously; the stability of hole transmission layer can be improved; the stability of photoelectric device is improved, promotes device performance while protecting device.

Description

A kind of preparation method based on polymer dielectric transport layer perovskite photovoltaic cell
Technical field
The invention belongs to organic photoelectric-area of solar cell, more particularly to one kind to be based on polymer dielectric transport layer The preparation method of perovskite photovoltaic cell.
Background technique
The energy is the important material guarantee that human society is depended on for existence and development, is the base of national economy and social development Plinth.With the increasingly exhausted and global concern to greenhouse effects of fossil energy, development and utilization clean reproducible energy just becomes The theme of present and future world energy science and technology development.Solar cell is a kind of using the sunlight direct generation of electricity, realizes photoelectricity The device and device of conversion summarize in this field, and the novel solar battery for studying high efficiency, low cost is to realize solar battery Widely used technical foundation.Perovskite solar battery is quickly grown in recent years due to its high photoelectric conversion efficiency, Unprecedented research boom is caused both at home and abroad, and has been achieved for many research achievements.A kind of high stability reported at present Monolithic perovskite/silicon series-connected solar cells photoelectric efficiency be up to 23.6%(KevinA. Bush, Zachary C. Holman, Michael D. McGehee et al. 23.6%-efficientmonolithic perovskite/ silicon tandem solar cells with improved stability. NatureEnergy 2017, 2, 17009.).Therefore, the research for actively developing perovskite solar battery is captured perspective in the field of this great potential Main strategy be of great significance to national economy duration from now on and innovative development.
Currently, Ca-Ti ore type solar battery mainly use transparent conductive electrode, electron transfer layer, perovskite light-absorption layer, Hole transmission layer and positive electrode composition.The hole transmission layer being widely used at present is mainly using with superior hole transmittability 2,2,7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes (Spiro-OMeTAD) is effective to improve The photoelectric properties of perovskite solar battery.But due to passing through [N, N- bis- (4- methoxyphenyl) ammonia of spin coating 2,2,7,7 '-four Base] -9,9 '-spiral shell, two fluorenes (Spiro-OMeTAD) prepares hole transport layer material, to porous TiO2Permeability of the membrane is poor, and interface connects It touches to be improved.And polymer electrolytic confrontation TiO2Perforated membrane has good permeance property and interface contact performance；Gather simultaneously The reticular structure for closing object can effectively prevent the volatilization of organic solvent, improve the stability of hole transmission layer.Chinese utility model is special Sharp 203883017 U of CN disclose it is a kind of using zinc telluridse as the preparation method of the perovskite solar battery of hole transmission layer, Provide the perovskite solar battery based on zinc telluridse inorganic material of low cost, but the limited transmittability in inorganic matter hole The photoelectric properties of perovskite solar battery are limited, 101555000 A of Chinese invention patent application CN provides a kind of base In the perovskite solar battery and preparation method thereof of Spiro-OMeTAD/PbS composite hole transporting layer, in Spiro-OMeTAD And to insertion lead sulfide film between electrode as buffer layer, but the buffer layer is to deposit lead sulfide film using thermal evaporation, Preparation process is complicated, and pyroprocess may will affect the organic solvents such as Spiro-OMeTAD, reduces perovskite solar battery Photoelectric properties.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art especially overcomes hole in the prior art Layer material is transmitted to porous TiO2Permeability of the membrane is poor, the bad deficiency of interfacial contact, provides a kind of good penetrability, easily forms a film Preparation method based on polymer dielectric transport layer perovskite photovoltaic cell.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method based on polymer dielectric transport layer perovskite photovoltaic cell, comprising the following steps:
(1) transparent FTO electro-conductive glass is cleaned, transparent conductive substrate is obtained；
(2) titanic oxide electronic transport layer is prepared in transparent conductive substrate；
(3) perovskite CH is prepared in the titanic oxide electronic transport layer obtained by step (2)3NH3PbX3Extinction layer film；
(4) preparation of polymer dielectric transport layer:
(4- I) weighs a certain amount of polymer substrate and is dissolved in chlorobenzene solvent, stirs evenly, and it is molten to obtain conducting polymer Liquid；It weighs a certain amount of bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI) simultaneously to be dissolved in acetonitrile solvent, stirs evenly, obtain To the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI)；
(4- II) weighs 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shells according to a certain percentage Gained bis trifluoromethyl sulfonic acid Asia amide lithium in two fluorenes (Spiro-OMeTAD), 4- tert .-butylpyridine (TBP) and step (4- I) Acetonitrile solution, be dissolved in conductive polymer solution obtained by step (4- I), stirred evenly under certain temperature, obtain perovskite Use polymer dielectric；
Step (4- II) resulting perovskite is added drop-wise to step (3) gained perovskite with polymer dielectric by (4- III) CH3NH3PbX3It on extinction layer film, is dried in drying box thick, that is, polymer dielectric transport layer is made；
(5) electrode will be covered in polymer dielectric transport layer, will be obtained based on polymer dielectric transport layer calcium titanium Mine photovoltaic cell.
In above-mentioned preparation method, it is preferred that in the step (1), cleaning way are as follows: deionized water, anhydrous is respectively adopted Ethyl alcohol, isopropanol ultrasonic vibration clean FTO electro-conductive glass, after concussion, using the organic machine group in ozone oxidation surface.
In above-mentioned preparation method, it is preferred that in the step (2), prepare the detailed process of titanic oxide electronic transport layer Are as follows: spin-coating method is used, by TiO2Slurry for rotary coating is allowed to be formed uniformly flat in the transparent conductive substrate surface cleaned up Whole film is placed in Muffle furnace through 450 DEG C~500 DEG C 30~60 min of high-temperature roasting to get titanic oxide electronic transport layer.
In above-mentioned preparation method, it is preferred that in the step (3), perovskite CH3NH3PbX3The preparation of extinction layer film Journey: by perovskite CH3NH3PbX3Solution is spin-coated in the resulting titanic oxide electronic transport layer of step (2), and is allowed to dry shape At film；The perovskite CH3NH3PbX3Solution be by mass percent be 60 ~ 80% dimethylformamide, 10 ~ 40% CH3NH3The PbX of X and 5 ~ 10%2Mixing it is obtained to stir 12 ~ 18h, wherein X=Cl, I or Br at 60 ~ 80 DEG C.
In above-mentioned preparation method, it is preferred that in the step (3), the perovskite CH3NH3PbX3The spin speed of solution For 2500 ~ 4000rpm, spin-coating time is 30 ~ 60s.
In above-mentioned preparation method, it is preferred that in the step (4), the preparation of polymer dielectric transport layer includes following Step:
In above-mentioned preparation method, it is preferred that in the step (4- I), the polymer substrate includes but is not limited to poly- 3- At least one of ethylthiophene (P3HT), poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] (PTAA) etc. are added Amount accounts for the 2 ~ 3% of chlorobenzene solvent quality；In the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium, bis trifluoromethyl sulfonic acid The concentration of sub- amide lithium is 500 ~ 600g/L, is stirred at room temperature.
In above-mentioned preparation method, it is preferred that in the step (4- II), 2,2 ', 7,7 '-four [(the 4- methoxybenzenes of N, N- bis- Base) amino] two fluorenes (Spiro-OMeTAD) of -9,9 '-spiral shell, 4- tert .-butylpyridine (TBP), the double fluoroforms of gained in step (4- I) The additional amount of the acetonitrile solution of base sulfonic acid Asia amide lithium, on the basis of the chlorobenzene solvent dosage in step (4- I), described 2,2 ', The additional amount of 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes is added 70 ~ 80 by every liter of chlorobenzene solvent The ratio of g calculates；The volume of the 4- tert .-butylpyridine (TBP) is the 3 ~ 4% of chlorobenzene solvent volume；The bis trifluoromethyl sulphur The volume of the acetonitrile solution of sour Asia amide lithium, is the 1.5 ~ 2% of chlorobenzene solvent volume；By gained mixed liquor under 60 ~ 70 DEG C of sand-baths Heating, stirring, control 12 ~ 24 h of mixing time.
In above-mentioned preparation method, it is preferred that in the step (4- III), the holding temperature in drying box is 30 ~ 40 DEG C, is protected The warm time is 10 ~ 30min, is dried to thick.
In above-mentioned preparation method, it is preferred that described to electrode or to gather for platinum to electrode, gold to electrode in the step (5) Aniline (PANI) is to electrode.
Compared with the prior art, the advantages of the present invention are as follows:
Using polymer dielectric as hole transmission layer, in link units containing can dissociative ion group, have The advantages that light, easy film forming, to TiO2Perforated membrane have good permeance property and interface contact performance, have good penetrability, The advantages that easily forming a film；The reticular structure of polymer can effectively prevent the volatilization of organic solvent simultaneously, can improve hole transmission layer Stability improves the stability of photoelectric device, promotes device performance while protecting device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the polymer dielectric transport layer perovskite photovoltaic cell of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment, But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or Person can the product as made from well known method.
Embodiment 1:
The preparation method based on polymer dielectric transport layer perovskite photovoltaic cell of the present embodiment, including following step It is rapid:
(1) preparation of transparent conductive substrate: transparent FTO electro-conductive glass is cleaned first.Be respectively adopted deionized water, Dehydrated alcohol, isopropanol carry out ultrasonic vibration, clean conductive glass surface, reapply ozone complete oxidation conductive glass surface Organic machine group.
(2) preparation of titanic oxide electronic transport layer: spin-coating method is used, by TiO2Slurry for rotary coating is in cleaning up Transparent conductive substrate surface, be allowed to form uniform ground film, be placed in Muffle furnace through 450 DEG C of high-temperature roasting 30min, formed TiO2Electron transfer layer (i.e. light anode layer).
(3) perovskite CH is prepared in the titanic oxide electronic transport layer obtained by step (2)3NH3PbX3Light-absorption layer: prepare with The chemicals of lower mass percent: 62% dimethylformamide, 32% CH3NH3The PbI of I and 6%2, by CH3NH3I and PbI2 It is separately added into organic solvent dimethylformamide, stirs 13h under 80 DEG C of constant temperature sand-baths, form uniform CH3NH3PbI3It is molten Liquid；
By the CH of preparation3NH3PbI3Solution is added drop-wise in the resulting titanic oxide electronic transport layer of step (2), is put into spin coating In machine, setting rotation speed to 3500rpm, rotational time 45s forms uniform perovskite in titanic oxide electronic transport layer CH3NH3PbX3Extinction layer film.
(4) preparation of polymer dielectric transport layer:
The preparation of the acetonitrile solution of (4- I) conductive polymer solution and bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI):
Poly- 3- ethylthiophene is dissolved in chlorobenzene solvent, the poly- 3- ethylthiophene is the 2% of chlorobenzene solvent quality, shake It swings to it and is completely dissolved uniformly, obtain conductive polymer solution；
Bis trifluoromethyl sulfonic acid Asia amide lithium is weighed simultaneously, is dissolved in acetonitrile solvent, so that bis trifluoromethyl in solution The concentration of sulfonic acid Asia amide lithium is 500g/L, and concussion is completely dissolved to it, obtains bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI) Acetonitrile solution.
The preparation of (4- II) liquid perovskite polymer dielectric: 2,2 ', 7,7 '-four [N, N- bis- are proportionally weighed (4- methoxyphenyl) amino] two fluorenes (Spiro-OMeTAD) of -9,9 '-spiral shell, 4- tert .-butylpyridine (TBP), institute in step (4- I) The acetonitrile solution for obtaining bis trifluoromethyl sulfonic acid Asia amide lithium is dissolved in conductive polymer solution obtained by step (4- I)；With step On the basis of chlorobenzene solvent dosage in (4- I), 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-are controlled The additional amount of two fluorenes of spiral shell is calculated in the ratio that 75g is added in every liter of chlorobenzene solvent；The volume of 4- tert .-butylpyridine (TBP) is that chlorobenzene is molten The 3.3% of agent volume；The volume of the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium is the 1.5% of chlorobenzene solvent volume； Gained mixed liquor is uniformly mixed, sand-bath heating, 14 h of stirring, obtain liquid perovskite polymer dielectric at 65 DEG C.
The preparation of (4- III) polymer dielectric transport layer: by liquid perovskite polymer electrolytic obtained by step (4- II) Matter is added drop-wise to perovskite CH obtained by step (3)3NH3PbX3On extinction layer film, it is placed in 30 DEG C of drying boxes and toasts 10min, be dried to Solution becomes sticky, that is, polymer dielectric transport layer is made；
(5) platinum the preparation of perovskite photovoltaic cell: is covered into the resulting sticky polymer of step (4- III) to electrode On electrolyte transport layer, obtain based on polymer dielectric transport layer perovskite photovoltaic cell.
Test the performance of the resulting perovskite photovoltaic cell based on polymer dielectric transport layer of the present embodiment: in room temperature Environment, using xenon lamp simulated solar irradiation, light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency It is 12%, stability test 500 hours, photoelectric efficiency was down to the 90% of initial value.
Embodiment 2:
The preparation method based on polymer dielectric transport layer perovskite photovoltaic cell of the present embodiment, including following step It is rapid:
(1) preparation of transparent conductive substrate: FTO electro-conductive glass is cleaned first.Deionized water, anhydrous is respectively adopted Ethyl alcohol, isopropanol carry out ultrasonic vibration, clean conductive glass surface, reapply the organic of ozone complete oxidation conductive glass surface Machine group；
(2) preparation of titanic oxide electronic transport layer: spin-coating method is used, by TiO2Slurry for rotary coating is in cleaning up Transparent conductive substrate surface, be allowed to form uniform ground film, be placed in Muffle furnace through 500 DEG C of 60 min of high-temperature roasting, shape At TiO2Titanic oxide electronic transport layer.
(3) perovskite CH is prepared in the titanic oxide electronic transport layer obtained by step (2)3NH3PbX3Extinction layer film: quasi- The chemicals of standby following mass percent: 70% dimethylformamide, 22% CH3NH3The PbI of I and 8%2, respectively will CH3NH3I and PbI2It is added in organic solvent dimethylformamide, stirs 15h under 75 DEG C of constant temperature sand-baths, form uniform calcium titanium Mine CH3NH3PbI3Solution；
By the perovskite CH of preparation3NH3PbI3Solution is added drop-wise in the resulting titanic oxide electronic transport layer of step (2), is put Enter in sol evenning machine, setting rotation speed to 4000 rpm, 50 s of rotational time, is formed in titanic oxide electronic transport layer uniform Perovskite CH3NH3PbI3Extinction layer film.
(4) preparation of polymer dielectric transport layer:
The preparation of the acetonitrile solution of (4- I) conductive polymer solution and bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI): It weighs poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] to be dissolved in chlorobenzene solvent, additional amount accounts for chlorobenzene solvent quality 2%, concussion be completely dissolved to it, stir evenly, obtain conductive polymer solution；Bis trifluoromethyl sulfonic acid Asia acyl is weighed simultaneously Amine lithium, is dissolved in acetonitrile solvent, and concussion is completely dissolved to it, stirs evenly, obtains bis trifluoromethyl sulfonic acid Asia amide lithium (LiTFSI) acetonitrile solution；In the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium, bis trifluoromethyl sulfonic acid Asia acyl The concentration of amine lithium is 550g/L.
The preparation of (4- II) liquid perovskite polymer dielectric: 2,2 ', 7,7 '-four [N, N- bis- are proportionally weighed (4- methoxyphenyl) amino] in two fluorenes (Spiro-OMeTAD) of -9,9 '-spiral shell, 4- tert .-butylpyridine (TBP) and step (4- I) The acetonitrile solution of gained bis trifluoromethyl sulfonic acid Asia amide lithium is dissolved in conductive polymer solution obtained by step (4- I), with step Suddenly on the basis of the chlorobenzene solvent dosage in (4- I), described 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9, The additional amount of 9 '-spiral shell, two fluorenes (Spiro-OMeTAD) is calculated in the ratio that 78 g are added in every liter of chlorobenzene solvent；The 4- tert-butyl The volume of pyridine (TBP) is the 4% of chlorobenzene solvent volume；The volume of the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium, It is the 2% of chlorobenzene solvent volume；Gained mixed liquor is uniformly mixed, sand-bath heats at 70 DEG C, stirs 20 h, obtains liquid calcium Titanium ore polymer dielectric.
The preparation of (4- III) polymer dielectric transport layer: by liquid perovskite polymer electrolytic obtained by step (4- II) Matter is added drop-wise to perovskite CH obtained by step (3)3NH3PbX3On extinction layer film, it is put into 40 DEG C of drying boxes and toasts 20min, in baking It is dried to thick in dry case, that is, polymer dielectric transport layer is made；
(5) preparation of polymer dielectric transport layer perovskite photovoltaic cell: resulting sticky poly- in step (4- III) Gold is covered in polymer electrolyte transport layer to electrode, is obtained based on polymer dielectric transport layer perovskite photovoltaic cell.
Test the performance of the resulting perovskite photovoltaic cell based on polymer dielectric transport layer of the present embodiment: in room temperature Environment, using xenon lamp simulated solar irradiation, light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency It is 9.7%；Stability test 500 hours, photoelectric efficiency was down to the 80% of initial value.
Comparative example:
This comparative example, in addition to step (4), other steps and embodiment 1 are identical.
It is added without the poly- 3- ethylthiophene (P3HT) of polymer substrate in step (4- I), is replaced using the chlorobenzene of phase homogenous quantities Conductive polymer solution；
In step (4- II), 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-are proportionally weighed Gained bis trifluoromethyl sulfonic acid Asia amide lithium in two fluorenes of spiral shell (Spiro-OMeTAD), 4- tert .-butylpyridine (TBP), step (4- I) Acetonitrile solution, be dissolved in step (4- I) chlorobenzene；On the basis of the chlorobenzene solvent dosage in step (4- I), control 2,2,7, The ratio of 75g is added by every liter of chlorobenzene solvent for the additional amount of 7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes Example calculates；The volume of 4- tert .-butylpyridine (TBP) is the 3.3% of chlorobenzene solvent volume；Bis trifluoromethyl sulfonic acid Asia amide lithium Acetonitrile solution volume, be chlorobenzene solvent volume 1.5%；Gained mixed liquor is uniformly mixed, at 65 DEG C sand-bath heating, 14 h are stirred, liquid hole mobile material is obtained.
(4- III) prepares hole transmission layer using the method for spin coating, and setting spin speed is 2500rpm, and spin-coating time is 30s is spin-coated to CH3NH3PbI3On extinction layer film.
Test the performance of the resulting perovskite photovoltaic cell of this comparative example: in room temperature environment, using xenon lamp simulated solar irradiation, Light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency be 6.1%；Stability test 10 hours, Photoelectric efficiency is down to the 20% of initial value.
To sum up, the preparation method provided by the present invention based on polymer dielectric transport layer perovskite photovoltaic cell is simple It is easy, using this method prepare polymer dielectric it is functional, can finally improve perovskite photovoltaic cell photoelectricity turn Change efficiency and stability.

Claims (9)

1. a kind of preparation method based on polymer dielectric transport layer perovskite photovoltaic cell, which is characterized in that including following Step:
(1) transparent FTO electro-conductive glass is cleaned, transparent conductive substrate is obtained；
(2) titanic oxide electronic transport layer is prepared in transparent conductive substrate；
(3) perovskite CH is prepared in the titanic oxide electronic transport layer obtained by step (2)3NH3PbX3Extinction layer film；
(4) preparation of polymer dielectric transport layer:
(4- I) weighs a certain amount of polymer substrate and is dissolved in chlorobenzene solvent, stirs evenly, and obtains conductive polymer solution； It weighs a certain amount of bis trifluoromethyl sulfonic acid Asia amide lithium simultaneously to be dissolved in acetonitrile solvent, stir evenly, obtain double fluoroforms The acetonitrile solution of base sulfonic acid Asia amide lithium；
The polymer substrate is poly- 3- ethylthiophene, at least one in poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] Kind, additional amount accounts for the 2 ~ 3% of chlorobenzene solvent quality；
(4- II) weigh according to a certain percentage 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes, The acetonitrile solution of gained bis trifluoromethyl sulfonic acid Asia amide lithium, is dissolved in step (4- in 4- tert .-butylpyridine and step (4- I) I) it in gained conductive polymer solution, is stirred evenly under certain temperature, obtains perovskite polymer dielectric；
Step (4- II) resulting perovskite is added drop-wise to step (3) gained perovskite with polymer dielectric by (4- III) CH3NH3PbX3It on extinction layer film, is dried in drying box thick, that is, polymer dielectric transport layer is made；
(5) electrode will be covered in polymer dielectric transport layer, will be obtained based on polymer dielectric transport layer perovskite light Lie prostrate battery.
2. the preparation method according to claim 1 based on polymer dielectric transport layer perovskite photovoltaic cell, special Sign is, in the step (1), cleaning way are as follows: deionized water, dehydrated alcohol, the cleaning of isopropanol ultrasonic vibration is respectively adopted FTO electro-conductive glass, after concussion, using the organic machine group in ozone oxidation surface.
3. the preparation method according to claim 1 or 2 based on polymer dielectric transport layer perovskite photovoltaic cell, It is characterized in that, in the step (2), prepares the detailed process of titanic oxide electronic transport layer are as follows: spin-coating method is used, it will TiO2Slurry for rotary coating is allowed to form uniform ground film, is placed in Muffle furnace and passes through in the transparent conductive substrate surface cleaned up 450 DEG C~500 DEG C 30~60 min of high-temperature roasting are to get titanic oxide electronic transport layer.
4. the preparation method according to claim 1 or 2 based on polymer dielectric transport layer perovskite photovoltaic cell, It is characterized in that, in the step (3), perovskite CH3NH3PbX3The preparation process of extinction layer film: by perovskite CH3NH3PbX3 Solution is spin-coated in the resulting titanic oxide electronic transport layer of step (2), and is allowed to drying and is formed film；The perovskite CH3NH3PbX3It is 60 ~ 80% dimethylformamide, 10 ~ 40% CH that solution, which is by mass percent,3NH3The PbX of X and 5 ~ 10%2 Mixing it is obtained to stir 12 ~ 18h, wherein X=Cl, I or Br at 60 ~ 80 DEG C.
5. the preparation method according to claim 4 based on polymer dielectric transport layer perovskite photovoltaic cell, special Sign is, in the step (3), the perovskite CH3NH3PbX3The spin speed of solution is 2500 ~ 4000rpm, spin-coating time For 30 ~ 60s.
6. the preparation method according to claim 1 or 2 based on polymer dielectric transport layer perovskite photovoltaic cell, It is characterized in that, in the step (4- I), in the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium, bis trifluoromethyl sulphur The concentration of sour Asia amide lithium is 500 ~ 600g/L, is stirred at room temperature.
7. the preparation method according to claim 1 or 2 based on polymer dielectric transport layer perovskite photovoltaic cell, It is characterized in that, in the step (4- II), 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes, The additional amount of the acetonitrile solution of gained bis trifluoromethyl sulfonic acid Asia amide lithium in 4- tert .-butylpyridine, step (4- I), with step On the basis of chlorobenzene solvent dosage in (4- I), described 2,2 ', 7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 ' - The additional amount of two fluorenes of spiral shell is calculated in the ratio that 70 ~ 80g is added in every liter of chlorobenzene solvent；The volume of the 4- tert .-butylpyridine is chlorobenzene The 3 ~ 4% of solvent volume；The volume of the acetonitrile solution of bis trifluoromethyl sulfonic acid Asia amide lithium is the 1.5 of chlorobenzene solvent volume ~2%；Gained mixed liquor is heated under 60 ~ 70 DEG C of sand-baths, is stirred, 12 ~ 24 h of mixing time is controlled.
8. the preparation method according to claim 1 or 2 based on polymer dielectric transport layer perovskite photovoltaic cell, It is characterized in that, in the step (4- III), the holding temperature in drying box is 30 ~ 40 DEG C, and soaking time is 10 ~ 30min, drying It is extremely thick.
9. the preparation method according to claim 1 or 2 based on polymer dielectric transport layer perovskite photovoltaic cell, Be characterized in that, in the step (5), it is described to electrode be platinum to electrode, gold to electrode or polyaniline to electrode.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104409636A (en) * 2014-11-18 2015-03-11 天津理工大学 Perovskite thin-film solar cell with three-dimensional ordered mesopore support layer
CN106025085A (en) * 2016-07-18 2016-10-12 武汉大学 Perovskite solar cell based on Spiro-OMeTAD/CuxS composite hole transport layer and preparation method thereof
CN106129252A (en) * 2016-07-18 2016-11-16 武汉大学 Perovskite solaode based on Spiro OMeTAD/PbS composite hole transporting layer and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104409636A (en) * 2014-11-18 2015-03-11 天津理工大学 Perovskite thin-film solar cell with three-dimensional ordered mesopore support layer
CN106025085A (en) * 2016-07-18 2016-10-12 武汉大学 Perovskite solar cell based on Spiro-OMeTAD/CuxS composite hole transport layer and preparation method thereof
CN106129252A (en) * 2016-07-18 2016-11-16 武汉大学 Perovskite solaode based on Spiro OMeTAD/PbS composite hole transporting layer and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Effective Electron Blocking of CuPC-Doped Spiro-OMeTAD for Highly Effi cient Inorganic–Organic Hybrid Perovskite Solar Cells;Jangwon Seo,et al;《Adv. Energy Mater.》;20150921;第5卷;全文
HIGH-EFFICIENT SOLID-STATE PEROVSKITE SOLAR CELL WITHOUT LITHIUM SALT IN THE HOLE TRANSPORT MATERIAL;DONGQIN BI,et al;《NANO: Brief Reports and Reviews》;20141231;第9卷(第5期);全文
Nanostructured TiO2/CH3NH3PbI3 heterojunction solar cells employing spiro-OMeTAD/Co-complex as hole-transporting material;Jun Hong Noh,et al;《J. Mater. Chem. A》;20130719;第1卷;全文

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